CN110707270A - Fiber alumina-based lithium ion battery ceramic diaphragm and preparation method thereof - Google Patents
Fiber alumina-based lithium ion battery ceramic diaphragm and preparation method thereof Download PDFInfo
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- CN110707270A CN110707270A CN201910928580.3A CN201910928580A CN110707270A CN 110707270 A CN110707270 A CN 110707270A CN 201910928580 A CN201910928580 A CN 201910928580A CN 110707270 A CN110707270 A CN 110707270A
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- ceramic
- separator
- alumina
- lithium ion
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a fiber alumina-based lithium ion battery ceramic diaphragm and a preparation method thereof. Compared with the prior art, the invention adopts the fiber alumina as the ceramic coating material of the diaphragm for the lithium ion battery for the first time, and the performance index of the fiber alumina completely meets the requirement of the ceramic diaphragm material; meanwhile, the mechanical property, the temperature resistance and the oxidation resistance of the material have advantages compared with the traditional materials such as alumina, titanium dioxide and the like; and the battery formed based on the ceramic diaphragm has better high-temperature resistance and mechanical safety, reduces the risk of lithium dendrite puncturing the diaphragm, and improves the cycle performance.
Description
Technical Field
The invention belongs to the technical field of preparation of battery diaphragm materials, and relates to a lithium ion battery ceramic diaphragm based on fiber alumina and a preparation method thereof.
Background
The lithium ion battery diaphragm determines the internal resistance and the interface structure of the battery, and further determines the characteristics of the battery such as capacity, safety performance, charge-discharge density and cycle performance. Meanwhile, the paint has good chemical stability and organic solvent resistance; good mechanical property, high tensile strength and high puncture strength; good thermal stability, low thermal shrinkage and high film breaking temperature; good electrolyte wettability, good compatibility with the electrolyte and high liquid absorption rate.
However, the conventional mainstream separator adopts a polyolefin organic separator such as PE, and then the melting point of the separator is low, the thermal stability of the separator is poor, and when the temperature of the battery is increased due to internal or external stimulation, the organic separator may shrink or melt, so that the positive and negative electrodes of the battery are short-circuited, and the battery is burnt or exploded. In addition, such organic separators are also easily oxidized by the positive electrode active material to affect the cycle performance of the battery.
In order to solve the problems of the existing polyolefin such as PE and the like which are accumulated in the organic diaphragm, research and development personnel propose that a ceramic coating is coated on the organic diaphragm. The ceramic coating diaphragm is prepared by taking PP, PE or multilayer composite diaphragms as a substrate, coating a layer of nano alumina material on the surface, and closely adhering the nano alumina material to the substrate through special process treatment. The high-temperature resistance and the safety of the lithium ion battery can be obviously improved.
According to the characteristics of the ceramic diaphragm, the main structural types are single-layer composite, double-layer composite, bulk composite, in-situ composite and full ceramic diaphragm. The main film forming processes include coating, electrostatic spinning, wet method, die pressing and high-temperature sintering. At present, Al is mainly used for preparing ceramic composite diaphragms2O3、SiO2、TiO2And BaTiO3And the like.
The alumina fiber belongs to high-performance inorganic fiber, is a polycrystalline ceramic fiber and has various forms of long fiber, short fiber, whisker and the like. The main component is Al2O3The other trace component is SiO2、B2O3、Zr2O3MgO, and the like. It has the advantages of high strength, high modulus, small heat conductivity, low thermal expansion coefficient, chemical erosion resistance, extraordinary heat resistance, high temperature oxidation resistance and the like, and also has the advantages of original structureThe material cost is low, the production process is simple, the cost performance and the commercial value are high, and the method is widely applied to the fields of industrial, military and civil composite materials.
Based on alumina fiber, the main component is Al2O3And the like, and has the characteristics of insulation, high Mohs hardness, corrosion resistance, high temperature resistance and the like, and meets the basic requirements of the ceramic diaphragm on coating materials.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a fiber alumina-based lithium ion battery ceramic diaphragm and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a fibrous alumina-based lithium ion battery ceramic separator includes a separator substrate, and a ceramic coating comprising alumina fibers coated on the separator substrate.
Further, the diaphragm substrate is any one of a single-layer PP diaphragm, a single-layer PE diaphragm, a double-layer PE/PP diaphragm, a double-layer PP/PP diaphragm, a three-layer PP/PE/PP diaphragm, a PET diaphragm, a PI diaphragm, a PMIA diaphragm and a PBO diaphragm.
Furthermore, the thickness of the diaphragm substrate is 5-30 μm.
Further, the ceramic coating is prepared by mixing and pulping components including a ceramic material containing alumina fibers, a binder and a dispersant.
Further, the ceramic material comprises alumina fiber and Al2O3、SiO2、TiO2Or BaTiO3One or more of (a).
More preferably, the mass content of the alumina fiber in the ceramic material is 0-100%.
Further, the binder comprises one or more of PVDF, SBR, CMC-Na, fluorine-containing olefin polymer, PI, PTFE and PAA. Preferably, when the solvent used for the ceramic coating is an organic solvent, the binder is an organic binder such as PVDF, and when the solvent is water, the organic binder such as PVDF may be selected, and an aqueous binder such as SBR or CMC-Na may also be selected.
In the invention, the adopted dispersant is only conventional and commercially available products in the field, and the dispersant mainly has the functions of reducing viscosity, thereby improving the production efficiency, increasing the content of the ceramic pigment and improving the leveling property of the ceramic coating.
Further, the particle size of the alumina fiber satisfies d50≤2μm。
A preparation method of a lithium ion battery ceramic diaphragm based on fiber alumina comprises the following steps:
(1) putting the dried binder into a solvent, stirring until no bubbles are generated, adding the dried ceramic material containing alumina fibers and a dispersing agent, and continuously stirring until the ceramic material and the dispersing agent are uniformly dispersed to obtain the ceramic coating;
(2) coating the ceramic coating on the diaphragm substrate by a coating machine in a coating room with a dew point not more than-40 ℃ to obtain a ceramic base film;
(3) and finally, carrying out vacuum drying treatment on the ceramic base film to obtain the target product ceramic diaphragm.
Further, in the step (1), the mass ratio of the ceramic material, the binder, the dispersant and the solvent is (30-50): (3-5): (3-5): (50-70);
in the step (2), the drying temperature is 60-100 ℃, preferably 80 ℃, and the time is 6-24 h.
Further, in the step (1), the drying treatment temperature is 120 ℃, and the time is 2-6 h.
Compared with the prior art, the invention has the following advantages:
1. the fibrous alumina is used as the ceramic coating material of the diaphragm for the lithium ion battery for the first time, and the performance index of the fibrous alumina completely meets the requirement of the ceramic diaphragm material;
2. the alumina fiber is used as the ceramic coating material of the diaphragm for the lithium ion battery, and the mechanical property, the temperature resistance and the oxidation resistance of the ceramic coating material have advantages compared with the traditional materials such as alumina, titanium dioxide and the like;
3. the lithium ion battery formed by the lithium ion battery ceramic diaphragm based on the fibrous alumina has better high temperature resistance and mechanical safety, reduces the risk that the lithium dendrite pierces the diaphragm, and improves the cycle performance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the starting materials and processing techniques used are conventional commercial starting materials and processing techniques in the art.
Example 1:
a fibrous alumina-based lithium ion battery ceramic separator includes a separator substrate, and a ceramic coating comprising alumina fibers coated on the separator substrate.
In this embodiment, the separator substrate is a single-layer PP separator.
The thickness of the diaphragm substrate is about 20 mu m.
The ceramic coating is prepared by mixing and pulping components including a ceramic material containing alumina fibers, a binder, a dispersant and a solvent.
The ceramic material is internally provided with alumina fiber and traditional Al2O3The mass content of the alumina fiber in the ceramic material is 0-100%.
The binder is organic binder such as PVDF.
The particle diameter of the alumina fiber satisfies d50≤2μm。
The preparation method of the ceramic diaphragm comprises the following specific steps:
(1) putting the adhesive and the ceramic material into a vacuum oven at 120 ℃, and drying for 3 hours for later use;
(2) putting the binder into a solvent, stirring until no bubbles are generated, adding the ceramic material containing alumina fibers and the dispersant, and continuously stirring until the ceramic material and the dispersant are uniformly dispersed to obtain the ceramic coating;
(2) coating the ceramic coating on the diaphragm substrate by a coating machine in a coating room with a dew point not more than-40 ℃ to obtain a ceramic base film;
(3) and finally, transferring the ceramic base membrane into a vacuum oven for drying treatment to obtain the target product ceramic diaphragm.
In the step (1), the mass ratio of the ceramic material, the binder, the dispersant and the solvent is (30-50): (3-5): (3-5): (50-70);
in the step (2), the drying temperature is 80 ℃ and the drying time is 12 h.
Comparative example 1
Compared with the embodiment 1, except that the ceramic material in the embodiment only adopts the traditional Al2O3In addition, the rest of the materials are unchanged.
Finally, comparing the performances of the ceramic diaphragm obtained in the embodiment 1 and the ceramic diaphragm obtained in the comparative example 1, it can be known that the ceramic diaphragm in the embodiment 1 improves the mechanical performance, the temperature resistance and the oxidation resistance on the premise of meeting the same function by introducing the alumina fiber into the ceramic diaphragm, and simultaneously greatly reduces the production cost, thereby having extremely high industrial application value.
Examples 2 to 9
Compared with the embodiment 1, the diaphragm substrate is mostly the same except that in the embodiment, the diaphragm substrate is respectively a single-layer PE diaphragm, a double-layer PE/PP diaphragm, a double-layer PP/PP diaphragm, a three-layer PP/PE/PP diaphragm, a PET diaphragm, a PI diaphragm, a PMIA diaphragm or a PBO diaphragm.
Example 10
Most of them were the same as in example 1 except that the thickness of the separator substrate was 5 μm in this example.
Example 11
Most of them were the same as in example 1 except that the thickness of the separator substrate was 30 μm in this example.
Example 12
Compared with the embodiment 1, the method is mostly the same, except that in the embodiment, the temperature for drying in the step (2) is 60 ℃ and the time is 24 h.
Example 13
Compared with the embodiment 1, the method is mostly the same, except that in the embodiment, the drying temperature in the step (2) is 100 ℃, and the drying time is 6 hours.
In the above embodiments, the conventional Al in the ceramic material2O3Can also be replaced by SiO2、TiO2Or BaTiO3Any one or any combination of two or more. The binder can also be replaced by any one or any two or more of SBR, CMC-Na, fluoro olefin polymer, PI, PTFE and PAA besides PVDF.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The ceramic separator based on fiber alumina for the lithium ion battery is characterized by comprising a separator substrate and a ceramic coating layer which is coated on the separator substrate and contains alumina fibers.
2. The fiber alumina-based lithium ion battery ceramic separator according to claim 1, wherein the separator substrate is any one of a single-layer PP separator, a single-layer PE separator, a double-layer PE/PP separator, a double-layer PP/PP separator, a triple-layer PP/PE/PP separator, a PET separator, a PI separator, a PMIA separator, or a PBO separator.
3. The fiber alumina-based lithium ion battery ceramic separator according to claim 1, wherein the thickness of the separator substrate is 5-30 μm.
4. The fiber alumina-based lithium ion battery ceramic separator according to claim 1, wherein the ceramic coating is prepared by mixing and pulping components including a ceramic material containing alumina fibers, a binder and a dispersant.
5. The fibrous alumina-based lithium ion battery ceramic separator according to claim 4, wherein the ceramic material comprises alumina fibers and Al2O3、SiO2、TiO2Or BaTiO3One or more of (a).
6. The fiber alumina-based lithium ion battery ceramic separator according to claim 5, wherein the mass content of alumina fibers in the ceramic material is 0-100%.
7. The fibrous alumina-based lithium ion battery ceramic separator of claim 4, wherein the binder comprises one or more of PVDF, SBR, CMC-Na, fluoroolefin polymer, PI, PTFE, PAA.
8. The fiber alumina-based lithium ion battery ceramic separator according to claim 1, wherein the particle size of the alumina fiber satisfies d50≤2μm。
9. The preparation method of the fiber alumina-based lithium ion battery ceramic separator according to any one of claims 1 to 8, comprising the following steps:
(1) putting the dried binder into a solvent, stirring until no bubbles are generated, adding the dried ceramic material containing alumina fibers and a dispersing agent, and continuously stirring until the ceramic material and the dispersing agent are uniformly dispersed to obtain the ceramic coating;
(2) coating the ceramic coating on the diaphragm substrate by a coating machine in a coating room with a dew point not more than-40 ℃ to obtain a ceramic base film;
(3) and finally, carrying out vacuum drying treatment on the ceramic base film to obtain the target product ceramic diaphragm.
10. The preparation method of the fiber alumina-based lithium ion battery ceramic separator is characterized in that in the step (1), the mass ratio of the ceramic material, the binder, the dispersant and the solvent is (30-50): (3-5): (3-5): (50-70);
in the step (2), the drying temperature is 60-100 ℃, and the drying time is 6-24 h.
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| CN201910928580.3A CN110707270A (en) | 2019-09-28 | 2019-09-28 | Fiber alumina-based lithium ion battery ceramic diaphragm and preparation method thereof |
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| CN201910928580.3A CN110707270A (en) | 2019-09-28 | 2019-09-28 | Fiber alumina-based lithium ion battery ceramic diaphragm and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113823829A (en) * | 2020-06-12 | 2021-12-21 | 厦门大学 | High-temperature-resistant lithium ion battery system and charging and discharging method thereof |
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- 2019-09-28 CN CN201910928580.3A patent/CN110707270A/en active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113823829A (en) * | 2020-06-12 | 2021-12-21 | 厦门大学 | High-temperature-resistant lithium ion battery system and charging and discharging method thereof |
| CN113823829B (en) * | 2020-06-12 | 2023-11-07 | 厦门大学 | High-temperature-resistant lithium ion battery system and charging and discharging method thereof |
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Application publication date: 20200117 |